EP0915916B1 - Solid nucleophilic reagent for conversion of benzylic halogen funnctionality on polymers to other functionalities - Google Patents

Solid nucleophilic reagent for conversion of benzylic halogen funnctionality on polymers to other functionalities Download PDF

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Publication number
EP0915916B1
EP0915916B1 EP97936268A EP97936268A EP0915916B1 EP 0915916 B1 EP0915916 B1 EP 0915916B1 EP 97936268 A EP97936268 A EP 97936268A EP 97936268 A EP97936268 A EP 97936268A EP 0915916 B1 EP0915916 B1 EP 0915916B1
Authority
EP
European Patent Office
Prior art keywords
solid
polymer
functionality
functionalities
benzylic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP97936268A
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German (de)
English (en)
French (fr)
Other versions
EP0915916A1 (en
Inventor
Chia Shian Chee
Hsien-Chang Wang
Kenneth William Powers
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Chemical Patents Inc
Original Assignee
ExxonMobil Chemical Patents Inc
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Filing date
Publication date
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Publication of EP0915916A1 publication Critical patent/EP0915916A1/en
Application granted granted Critical
Publication of EP0915916B1 publication Critical patent/EP0915916B1/en
Anticipated expiration legal-status Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/18—Introducing halogen atoms or halogen-containing groups
    • C08F8/20—Halogenation
    • C08F8/22—Halogenation by reaction with free halogens
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • a benzylic halogen functionality constitutes a very active electrophile which will react under suitable conditions with any nucleophile capable of donating electrons to it.
  • Suitable nucleophiles include those containing oxygen, sulfur, nitrogen, sodium, and potassium.
  • Equally important to this versatility in types of nucleophiles which will react with the benzylic halogen functionality, is the relatively mild conditions under which these nucleophilic substitution reactions proceed so that substitution reactions can be completed to introduce the desired functionality without cleavage or cross-linking reactions involving the saturated hydrocarbon backbone.
  • esters manufactured containing other functional groups such as acetate, stearate, linoleate, eleostearate, acrylate, cinnamate.
  • hydroxyl attached directly in place of the benzylic bromine or attached via another linkage
  • carboxy (4) nitrile; (5) quaternary ammonium salts; (6) quaternary phosphonium salts; (7) s-isothiuronium salts; (8) dithiocarbamate esters; and (9) mercaptans.
  • the reagent(s) preferably comprise(s) a solid nucleophile reagent containing oxygen, sulfur, nitrogen, phosphorous, carbon, silicon, magnesium, lithium, sodium, and potassium.
  • the nucleophilic substitution reaction utilizing the present invention takes place between a solid phase and a liquid phase.
  • the solid phase contains a nucleophilic agent whereas the liquid phase contains a polymer having a good leaving group.
  • the nucleophilic agent from the solid is transported to the polymer and simultaneously the leaving group from the polymer is re-incorporated to the solid.
  • the ion exchange proceeds through a S N 2 mechanism.
  • Solvents that are considered appropriate for the prevent invention include: THF, toluene, hydrocarbon (pentane. hexane, cycolohexane, heptane), benzene, carbon tetrachloride, and chloroform.
  • the nucleophilic substitution reaction can be affected in a temperature range between ambient temperature and solvent reflux temperature.
  • the molar ratio of the nucleophile agent on the solid to the leaving group on the polymer can range from 0.5:1 to 50:1.

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
EP97936268A 1996-08-01 1997-07-30 Solid nucleophilic reagent for conversion of benzylic halogen funnctionality on polymers to other functionalities Expired - Lifetime EP0915916B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US2304496P 1996-08-01 1996-08-01
US23044P 1996-08-01
PCT/US1997/013271 WO1998005692A1 (en) 1996-08-01 1997-07-30 Solid nucleophilic reagent for conversion of benzylic halogen funnctionality on polymers to other functionalities

Publications (2)

Publication Number Publication Date
EP0915916A1 EP0915916A1 (en) 1999-05-19
EP0915916B1 true EP0915916B1 (en) 2001-09-12

Family

ID=21812810

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97936268A Expired - Lifetime EP0915916B1 (en) 1996-08-01 1997-07-30 Solid nucleophilic reagent for conversion of benzylic halogen funnctionality on polymers to other functionalities

Country Status (16)

Country Link
US (2) US6156810A (hu)
EP (1) EP0915916B1 (hu)
JP (1) JP2000515577A (hu)
KR (1) KR20000029663A (hu)
CN (1) CN1226259A (hu)
AT (1) AT406374B (hu)
BR (1) BR9710903A (hu)
CA (1) CA2259252A1 (hu)
CZ (1) CZ428098A3 (hu)
DE (1) DE69706691T2 (hu)
EA (1) EA199900171A1 (hu)
ES (1) ES2160360T3 (hu)
HU (1) HUP9904507A3 (hu)
PL (1) PL331317A1 (hu)
TW (1) TW404957B (hu)
WO (1) WO1998005692A1 (hu)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2563599A (en) * 1999-02-04 2000-08-25 Dow Chemical Company, The Functionalized ethylene/vinyl or vinylidene aromatic interpolymers
US6313252B1 (en) 1999-02-04 2001-11-06 The Dow Chemical Company Functionalized ethylene/vinyl or vinylidene aromatic interpolymers
US6300431B1 (en) * 1999-12-17 2001-10-09 Exxonmobil Chemical Patents Inc. Phase transfer process with catalyst recovery
WO2003046019A1 (en) * 2001-11-26 2003-06-05 E. I. Du Pont De Nemours And Company Supported bis(phosphorus)ligands and their use in the catalysis
CA2551997C (en) * 2005-08-26 2014-05-27 Lanxess Inc. Novel methods for the preparation of butyl graft copolymers
EP3898716A4 (en) * 2018-12-21 2023-01-11 Arlanxeo Singapore Pte. Ltd. HALOGEN RECOVERY IN A WET PROCESS FOR HALOGENATION OF UNSATURATED ISOOLEFIN COPOLYMERS
CN110028609A (zh) * 2019-04-02 2019-07-19 天津南开和成科技有限公司 一种固体高分子亲核试剂及其制备方法

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3708462A (en) * 1971-04-08 1973-01-02 Dow Chemical Co Cross-linked styrylphosphine resins
US4039485A (en) * 1973-11-02 1977-08-02 Marathon Oil Company Ion exchange of metals from aqueous solutions using compositions of synthetic resins reacted with polyisocyanurate salts
CA1149998A (en) * 1978-06-27 1983-07-12 Jean E.E. Herbin Process for preparation of anion exchange resins with high density by bromination of crosslinked vinyltoluene copolymers
US4322501A (en) * 1980-09-22 1982-03-30 Monsanto Company Quaternization process for ion exchange membranes
US4461876A (en) * 1982-09-09 1984-07-24 Columbia University Polymeric reagents for the isolation and protection of carbonyl compounds
JPS62225513A (ja) * 1986-03-26 1987-10-03 Shin Etsu Chem Co Ltd ブロツク・グラフト共重合体及びその製造法
US5162445A (en) * 1988-05-27 1992-11-10 Exxon Chemical Patents Inc. Para-alkylstyrene/isoolefin copolymers and functionalized copolymers thereof
ATE140465T1 (de) * 1989-10-03 1996-08-15 Exxon Chemical Patents Inc Elastomere pfropfcopolymere und ihre verwendung als kompatibilisierungsmittel
US5203982A (en) * 1989-10-16 1993-04-20 Ionics, Incorporated Cation exchange membranes
JP2640039B2 (ja) * 1991-03-25 1997-08-13 エクソン・ケミカル・パテンツ・インク イソモノオレフィンとアルキルスチレンのグラフトポリマー
MX9205991A (es) * 1991-10-17 1993-12-01 Exxon Chemical Patents Inc Copolimeros isoolefinicos curables por radiacion.
US5461118A (en) * 1993-04-06 1995-10-24 Exxon Chemical Patents Inc. Para-alkylstyrene/isoolefin copolymers functionalized with an amine alkylthioethers or hydroxy-alkylthioethers and their use in polymer blends
DE69410475T2 (de) * 1993-09-17 1998-11-05 Exxon Research Engineering Co Neue funktionalisierte isoolefin/para-alkylstyrol copolymere
EP0705810A3 (en) * 1994-09-22 1997-04-09 Shell Int Research Process for cleaning starting materials for metal-catalyzed reactions and cleaning agents that can be used therefor
EP0787157B1 (en) * 1994-10-17 2000-12-20 Infineum USA L.P. Oleaginous compositions comprising grafted isomonoolefin alkylstyrene polymers

Also Published As

Publication number Publication date
EP0915916A1 (en) 1999-05-19
US6372858B1 (en) 2002-04-16
CA2259252A1 (en) 1998-02-12
HUP9904507A2 (hu) 2000-05-28
PL331317A1 (en) 1999-07-05
WO1998005692A1 (en) 1998-02-12
AT406374B (de) 2000-04-25
CZ428098A3 (cs) 1999-03-17
TW404957B (en) 2000-09-11
ES2160360T3 (es) 2001-11-01
KR20000029663A (ko) 2000-05-25
US6156810A (en) 2000-12-05
CN1226259A (zh) 1999-08-18
HUP9904507A3 (en) 2001-01-29
JP2000515577A (ja) 2000-11-21
ATA908597A (de) 1999-09-15
DE69706691D1 (de) 2001-10-18
EA199900171A1 (ru) 1999-08-26
BR9710903A (pt) 1999-08-17
DE69706691T2 (de) 2002-06-20

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